CN109659605B - Self-repairing polymer electrolyte matrix and preparation method thereof, self-repairing polymer electrolyte, lithium ion battery and application thereof - Google Patents

Self-repairing polymer electrolyte matrix and preparation method thereof, self-repairing polymer electrolyte, lithium ion battery and application thereof Download PDF

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CN109659605B
CN109659605B CN201811540502.8A CN201811540502A CN109659605B CN 109659605 B CN109659605 B CN 109659605B CN 201811540502 A CN201811540502 A CN 201811540502A CN 109659605 B CN109659605 B CN 109659605B
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唐永炳
张帆
王勇
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Shenzhen Institute of Advanced Technology of CAS
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
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    • H01M2300/0025—Organic electrolyte
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract

The invention provides a self-repairing polymer electrolyte matrix and a preparation method thereof, a self-repairing polymer electrolyte, a lithium ion battery and application thereof, and belongs to the technical field of self-repairing polymer electrolytes. The invention provides a self-repairing polymer electrolyte, wherein a self-repairing polymer electrolyte matrix comprises an inorganic nano additive, self-repairing polyurethane and other polymers; wherein, the inorganic nano additive and other polymers are grafted on the self-repairing polyurethane; the self-repairing polyurethane is obtained through a Diels-Alder reaction. The reversible action of a furan-maleimide structure in the self-repairing polyurethane enables a self-repairing polymer electrolyte matrix to have good self-repairing capability; the polymer electrolyte enables the self-repairing polymer electrolyte matrix to have good ionic conductivity; the inorganic nano additive provides active sites, so that the polymer is easy to form a three-dimensional cross-linked structure, and the ionic conductivity is further improved.

Description

Self-repairing polymer electrolyte matrix and preparation method thereof, self-repairing polymer electrolyte, lithium ion battery and application thereof
Technical Field
The invention belongs to the technical field of self-repairing polymer electrolytes, and particularly relates to a self-repairing polymer electrolyte matrix and a preparation method thereof, a self-repairing polymer electrolyte, a lithium ion battery and application thereof.
Background
The lithium ion battery has the advantages of high energy density, small volume, long service life and the like, and has wide application prospect in the fields of portable electronic equipment, electric automobiles and the like as an energy storage device. With the rapid development of wearable electronic devices, the development of lithium ion batteries with good flexibility has become a hot spot of people's attention. Due to the complexity of the use environment, the safety and reliability of the flexible lithium ion battery are required to be higher, because various external stimuli and physical damages are inevitably encountered in practical application, and physical damages such as bending, torsion, stretching and shearing can cause irreversible functional obstacles of the energy storage device, even cause severe environmental and safety problems such as electrolyte leakage and explosion.
At present, few research reports on self-repairing polymer electrolytes at home and abroad are provided, and self-repairing hydrogel electrolytes applied to water-system supercapacitors and water-system lithium ion batteries are mainly researched and developed. Although it has good self-repairing performance, the range of the working voltage window of the water-based polymer electrolyte is limited (less than 2V), so that the energy density of the energy storage device is not high.
In view of this, the invention is particularly proposed.
Disclosure of Invention
A first object of the present invention is to provide a self-healing polymer electrolyte matrix; the self-repairing polymer electrolyte matrix can be used for preparing a self-repairing polymer electrolyte with high working voltage, excellent electrochemical performance and good self-repairing performance, and can overcome the problems or at least partially solve the technical problems.
The second purpose of the invention is to provide a preparation method of the self-repairing polymer electrolyte matrix.
The third purpose of the invention is to provide a self-repairing polymer electrolyte which comprises the self-repairing polymer electrolyte matrix.
The fourth purpose of the invention is to provide a preparation method of the self-repairing polymer electrolyte.
A fifth object of the present invention is to provide a lithium ion battery, comprising the self-repairing polymer electrolyte; the lithium ion battery has good flexibility, self-repairing performance and higher energy density.
A sixth object of the present invention is to provide an application of the above lithium ion battery to an electronic device, an electric tool, or an electric vehicle.
According to a first aspect of the present invention, there is provided a self-healing polymer electrolyte matrix comprising an inorganic nano-additive, a self-healing polyurethane and other polymers;
wherein the inorganic nano-additive and other polymers are grafted onto the self-healing polyurethane;
the self-repairing polyurethane is obtained through a Diels-Alder reaction;
preferably, the Diels-Alder reaction is a furan/maleimide Diels-Alder cycloaddition reaction;
preferably, the furan ring graft modified polyurethane is obtained by grafting the furan derivative on the polyurethane, and then the furan ring graft modified polyurethane and the maleimide derivative are subjected to Diels-Alder reaction to obtain self-repairing polyurethane;
wherein the terminal groups of the polyurethane comprise isocyanate groups.
Preferably, the functional group of the furan derivative includes at least one of amino, hydroxyl, and carbamate;
preferably, the furan derivative comprises at least one of 2, 5-furandimethanol, trifuryl diol, furfuryl alcohol, furfuryl amine, furan ring-terminated polyurethane prepolymer and 1, 6-hexamethylene-bis (2-furylmethyl carbamate), preferably 2, 5-furandimethanol and/or trifuryl diol;
preferably, the maleimide derivative comprises polymaleimide and/or hydroxyl-containing mono-maleimide, preferably bismaleimide and/or hydroxyl-containing mono-maleimide;
preferably, the maleimide derivative comprises at least one of N-hydroxyethyl maleimide, N '- (4, 4' -methylenediphenyl) bismaleimide, M-600-maleimide, D-400-maleimide and T-403-maleimide, preferably N-hydroxyethyl maleimide and/or N, N '- (4, 4' -methylenediphenyl) bismaleimide.
Preferably, the inorganic nano additive comprises graphene oxide, carbon nano tube and nano Al2O3Nano SiO2And nano TiO2Preferably graphene oxide;
and/or, the other polymer comprises any one of PVDF, PVDF-HFP, PEO or PAN, or a composite comprising any one of the foregoing, preferably PVDF-HFP;
preferably, the mass fraction of the inorganic nano additive is 0% -10%, preferably 0.5% -5%, and further preferably 0.8% -1.5%;
preferably, the mass fraction of the self-repairing polyurethane is 30% -60%, preferably 40% -50%;
preferably, the mass fraction of the further polymer is from 30% to 60%, preferably from 40% to 50%.
According to a second aspect of the present invention, there is provided a method for preparing the self-repairing polymer electrolyte matrix, comprising the steps of:
grafting the inorganic nano additive and other polymers on the self-repairing polyurethane to obtain the self-repairing polymer electrolyte matrix.
Preferably, the preparation method of the self-repairing polymer electrolyte matrix comprises the following steps:
(a) dissolving an inorganic nano additive in an organic solvent, then adding diisocyanate, and reacting to obtain a modified inorganic nano additive;
(b) adding a dihydroxy compound into the solution obtained in the step (a), and reacting to obtain polyurethane grafted with an inorganic nano additive;
(c) adding a furan derivative to step (b) to graft the furan derivative onto the polyurethane obtained in step (b);
(d) adding a maleimide derivative into the step (c) to enable the maleimide derivative and a furan derivative to generate Diels-Alder reaction, so as to obtain self-repairing polyurethane with dynamic covalent bonds;
(e) dissolving other polymers in an organic solvent, adding the solution obtained in the step (d) to graft the other polymers on the self-repairing polyurethane obtained in the step (d), coating the self-repairing polyurethane on the surface of the substrate, and removing the solvent to obtain a self-repairing polymer electrolyte matrix;
preferably, in step (a), the organic solvent comprises an amide-based organic solvent, preferably N, N-dimethylformamide;
and/or, in step (a), the diisocyanate comprises at least one of 4,4 '-methylenebis (phenyl isocyanate), toluene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and lysine diisocyanate, preferably 4, 4' -methylenebis (phenyl isocyanate);
and/or in the step (a), the reaction temperature is 75-95 ℃, the reaction time is 2-4h, and the reaction gas atmosphere is nitrogen;
and/or in the step (a), the feeding ratio of the inorganic nano additive, the organic solvent and the diisocyanate is 0-22: 40-60: 6-10mg/mL/mmol, preferably 20: 50: 8 mg/mL/mmol;
and/or, in step (b), the dihydroxy compound comprises a polyether polyol, preferably polytetrahydrofuran diol, more preferably polytetrahydrofuran diol with a number average molecular weight of 1500-2500;
and/or in the step (b), the reaction temperature is 75-95 ℃, the reaction time is 2-4h, and the reaction gas atmosphere is nitrogen;
and/or, in step (b), the molar ratio of the dihydroxy compound to the diisocyanate is 1: 1.8-2.5, preferably 1: 2;
and/or in the step (c), the grafting temperature is 75-95 ℃, the grafting time is 2-4h, and the grafting gas atmosphere is nitrogen;
and/or, in step (c), the molar ratio of furan derivative to diisocyanate is 6-6.5: 8, preferably 6.25: 8;
and/or in the step (d), the reaction temperature is 75-95 ℃, the reaction time is 12-38h, and the gas atmosphere of the reaction is nitrogen;
and/or, in step (d), the molar ratio of maleimide derivative to furan derivative is 4-4.5: 6-6.5, preferably 4.2: 6.25;
and/or, in step (e), the organic solvent comprises an amide organic solvent, preferably N, N-dimethylformamide;
and/or, in the step (e), the grafting temperature is 60-100 ℃, and the grafting time is 1-12 h;
and/or, in the step (e), the weight ratio of the other polymer to the self-repairing polyurethane is 30-60: 30-60, preferably 40-50: 40-50.
According to a third aspect of the invention, a self-repairing polymer electrolyte is provided, which comprises the self-repairing polymer electrolyte matrix or the self-repairing polymer electrolyte matrix obtained by the preparation method, electrolyte salt and a solvent.
Preferably, the electrolyte salt includes a lithium salt, preferably at least one of lithium hexafluorophosphate, lithium perchlorate, lithium tetrafluoroborate, lithium acetate, lithium salicylate, lithium acetoacetate, lithium carbonate, lithium trifluoromethanesulfonate, lithium dodecylsulfate, lithium citrate, lithium bis (trimethylsilyl) amide, lithium hexafluoroarsenate, and lithium trifluoromethanesulfonylimide, and further preferably lithium hexafluorophosphate;
preferably, the solvent comprises an organic solvent or an ionic liquid;
preferably, the organic solvent includes at least one of an ester solvent, a sulfone solvent, an amide solvent, an ether solvent, and a nitrile solvent;
preferably, the ester-based solvent includes at least one of propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, butylene carbonate, dipropyl carbonate, methyl propyl carbonate, dibutyl carbonate, methyl butyl carbonate, methyl isopropyl carbonate, methyl ester, methyl formate, methyl acetate, fluoroethylene carbonate, methyl propionate, ethyl acetate, γ -butyrolactone, ethylene sulfite, propylene sulfite, dimethyl sulfite, and diethyl sulfite, preferably at least one of propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, and ethyl methyl carbonate;
preferably, the sulfone-based solvent comprises dimethyl sulfone;
preferably, the amide-based solvent includes N, N-dimethylacetamide;
preferably, the ether solvent includes at least one of tetrahydrofuran, 2-methyltetrahydrofuran, 1, 3-dioxolane, 4-methyl-1, 3-dioxolane, dimethoxymethane, 1, 2-dimethoxyethane, 1, 2-dimethoxypropane, triethylene glycol dimethyl ether, and crown ether;
preferably, the ionic liquid comprises 1-ethyl-3-methylimidazole-tetrafluoroborate, 1-ethyl-3-methylimidazole-hexafluorophosphate, 1-ethyl-3-methylimidazole-bistrifluoromethylsulfonyl imide salt, 1-propyl-3-methylimidazole-tetrafluoroborate, 1-propyl-3-methylimidazole-hexafluorophosphate, 1-propyl-3-methylimidazole-bistrifluoromethylsulfonyl imide salt, 1-butyl-1-methylimidazole-hexafluorophosphate, 1-butyl-1-methylimidazole-tetrafluoroborate, 1-butyl-1-methylimidazole-bistrifluoromethylsulfonyl imide salt, 1-ethyl-3-methylimidazole-hexafluoro-phosphate, 1-butyl-1-methylimidazole-bistrifluoromethylsulfonyl imide salt, a salt of N-methyl-ethyl-3-methylimidazole-hexafluorophosphate, a, At least one of N-butyl-N-methylpyrrolidine-bistrifluoromethylsulfonyl imide salt, 1-butyl-1-methylpyrrolidine-bistrifluoromethylsulfonyl imide salt, N-methyl-N-propylpyrrolidine-bistrifluoromethylsulfonyl imide salt, N-methyl, propylpiperidine-bistrifluoromethylsulfonyl imide salt, and N-methyl, butylpiperidine-bistrifluoromethylsulfonyl imide salt;
preferably, the concentration of the electrolyte salt in the electrolyte is 0.1 to 10mol/L, preferably 1 mol/L.
According to a fourth aspect of the present invention, there is provided a method for preparing the self-repairing polymer electrolyte, comprising the steps of:
and immersing the self-repairing polymer electrolyte matrix in a solvent containing electrolyte salt, and adsorbing until the self-repairing polymer electrolyte matrix is saturated to obtain the self-repairing polymer electrolyte.
According to a fifth aspect of the present invention, there is provided a lithium ion battery comprising the self-healing polymer electrolyte described above, a positive electrode, and a negative electrode.
Preferably, the active material of the positive electrode includes at least one of lithium iron phosphate, lithium cobaltate, lithium manganate, lithium vanadium phosphate, lithium nickel cobalt manganate, and lithium nickel cobalt aluminate;
preferably, the active material of the negative electrode includes at least one of metallic lithium flakes, graphite, mesocarbon fibers, mesocarbon microbeads, soft carbon, hard carbon, and silicon carbon composite.
According to a sixth aspect of the present invention, there is provided use of the above lithium ion battery in an electronic device, an electric tool, or an electric vehicle;
preferably, the electronic device is a wearable electronic device.
The invention provides a self-repairing polymer electrolyte matrix which comprises an inorganic nano additive, self-repairing polyurethane and other polymers. The reversible action of a furan-maleimide structure in the self-repairing polyurethane enables a self-repairing polymer electrolyte matrix to have good self-repairing capability; other polymers enable the self-repairing polymer electrolyte matrix to have good ionic conductivity; the inorganic nano additive provides active sites, so that the polymer is easy to form a three-dimensional cross-linked structure, and the ionic conductivity is further improved.
The self-repairing polymer electrolyte containing the self-repairing polymer electrolyte matrix has high working voltage, excellent electrochemical performance and good self-repairing performance.
The lithium ion battery obtained by the self-repairing polymer electrolyte has good flexibility and self-repairing performance and higher energy density, and the safety and reliability of the flexible lithium ion battery are improved, so that the stability of energy storage and release of the flexible lithium ion battery in an extreme environment is better, and the lithium ion battery has a wide application prospect in the field of wearable electronic equipment.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
It should be noted that:
in the present invention, all the embodiments and preferred methods mentioned herein can be combined with each other to form a new technical solution, if not specifically stated.
In the present invention, all the technical features mentioned herein and preferred features may be combined with each other to form a new technical solution, if not specifically stated.
In the present invention, the percentage (%) or parts means the weight percentage or parts by weight with respect to the composition, if not otherwise specified.
In the present invention, the components referred to or the preferred components thereof may be combined with each other to form a novel embodiment, if not specifically stated.
In the present invention, unless otherwise stated, the numerical range "a-b" represents a shorthand representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, a numerical range of "0% -10%" indicates that all real numbers between "0% -10%" have been listed herein, and "0% -10%" is a shorthand representation of the combination of these numbers.
The "ranges" disclosed herein may have one or more lower limits and one or more upper limits, respectively, in the form of lower limits and upper limits.
In the present invention, unless otherwise specified, the individual reactions or operation steps may be performed sequentially or may be performed in sequence. Preferably, the reaction processes herein are carried out sequentially.
Unless otherwise defined, technical and scientific terms used herein have the same meaning as is familiar to those skilled in the art. In addition, any methods or materials similar or equivalent to those described herein can also be used in the present invention.
According to a first aspect of the present invention, there is provided a self-healing polymer electrolyte matrix comprising an inorganic nano-additive, a self-healing polyurethane and other polymers;
wherein, the inorganic nano additive and other polymers are grafted on the self-repairing polyurethane;
the self-repairing polyurethane is obtained through a Diels-Alder reaction.
"other polymer" means a polymer other than a self-healing polyurethane, simply referred to as "other polymer".
The term "inorganic nano-additive and other polymers grafted on the self-repairing polyurethane" means that the inorganic nano-additive reacts with isocyanate groups on the self-repairing polyurethane to be grafted on the self-repairing polyurethane, for example, the inorganic nano-additive can react with monomeric diisocyanate of polyurethane to obtain a modified inorganic nano-additive, and then the modified inorganic nano-additive, diisocyanate and dihydroxy compound react to graft the inorganic nano-additive on the polyurethane; other polymers can form hydrogen bonds and other interactions with functional groups such as oxygen-containing functional groups and the like so as to be crosslinked with the self-repairing polyurethane.
The self-repairing polyurethane is obtained through Diels-Alder reaction, which means that the self-repairing polyurethane obtained through the Diels-Alder reaction contains dynamic covalent bonds capable of self-repairing.
The Diels-Alder reaction is not particularly limited, and for example, the Diels-Alder cycloaddition reaction may be furan/maleimide Diels-Alder cycloaddition reaction, and in this case, the self-repairing polyurethane obtained by the Diels-Alder cycloaddition reaction of furan/maleimide is furan-maleimide structural self-repairing polyurethane, that is, the self-repairing polyurethane having a dynamic covalent bond is obtained by the Diels-Alder reaction of a furan derivative and maleimide. The self-repairing polyurethane realizes self-repairing through a dynamic covalent bond, and the dynamic covalent bond is obtained by Diels-Alder reaction of a furan derivative and a maleimide derivative, namely the furan-maleimide structural self-repairing polyurethane.
It should be noted that, the present invention has no particular limitation on the source of the inorganic nano-additive, and the inorganic nano-additive for the battery, which is well known to those skilled in the art, may be used; for example, the material can be graphene oxide, carbon nano-tube, nano Al2O3Nano SiO2Or nano TiO2。
It should be noted that the present invention is not limited to the source of other polymers, and other polymers that can be used in the battery, which are well known to those skilled in the art, may be used; for example, it may be any one of PVDF-HFP, PVDF, PEO, or PAN, or a composite material including any one of the foregoing materials.
PVDF is shorthand for polyvinylidene fluoride, PVDF-HFP is shorthand for poly (vinylidene fluoride-hexafluoropropylene) copolymer, PEO is shorthand for polyethylene oxide, and PAN is shorthand for polyacrylonitrile.
The reversible action of a furan-maleimide structure in the self-repairing polyurethane enables a self-repairing polymer electrolyte matrix to have good self-repairing capability; other polymers enable the self-repairing polymer electrolyte matrix to have good ionic conductivity; the inorganic nano additive provides active sites, so that the polymer is easy to form a three-dimensional cross-linked structure, and the ionic conductivity is further improved.
In one embodiment, the furan ring graft modified polyurethane is obtained by grafting the furan derivative on the polyurethane, and then the furan ring graft modified polyurethane and the maleimide derivative are subjected to Diels-Alder reaction to obtain self-repairing polyurethane;
wherein the terminal group of the polyurethane comprises isocyanate.
The phrase "grafting furan derivatives to polyurethane to obtain furan ring graft-modified polyurethane" means that the furan derivatives react with terminal isocyanate groups on the polyurethane to graft on the polyurethane without destroying the furan ring after grafting, i.e., the obtained polyurethane contains furan rings.
The kind of the furan derivative is not particularly limited, and a furan derivative which can be grafted on polyurethane and does not destroy furan rings after grafting, which is conventional in the art, can be used. Furan derivatives include, but are not limited to, those containing functional groups that can react with isocyanate groups on the polyurethane without reaction disruption of the furan ring; functional groups that can react with isocyanate groups on the polyurethane include, but are not limited to, amino, hydroxyl, or carbamate. For example, furan derivatives include, but are not limited to, 2, 5-furandimethanol, trifuryl diol, furfuryl alcohol, furfuryl amine, furan ring-terminated polyurethane prepolymers, or 1, 6-hexamethylene-bis (2-furylmethyl carbamate).
The kind of the maleimide derivative is not particularly limited, and a maleimide derivative which is conventionally used in the art and can undergo a Diels-Alder reaction with a furan ring can be used. The maleimide derivative may be mono-maleimide containing hydroxyl group or polymaleimide. Maleimide derivatives include, but are not limited to, N-hydroxyethylmaleimide, N '- (4, 4' -methylenediphenyl) bismaleimide, M-600-maleinamide, D-400-maleinamide, or T-403-maleinamide.
The structural formula of the M-600-maleamide is as follows:
Figure BDA0001906659990000111
the structural formula of the D-400-maleamide is as follows:
Figure BDA0001906659990000121
the structural formula of the T-403-maleic amide is as follows:
Figure BDA0001906659990000122
in one embodiment, the furan derivative is 2, 5-furandimethanol and/or a trifuryl diol.
When the self-repairing polyurethane obtained by grafting 2, 5-furandimethanol and/or trifuryl diol on polyurethane and then carrying out Diels-Alder reaction with maleimide derivatives is used for preparing a lithium ion battery, the obtained battery has more excellent ionic conductivity, cycle number and self-repairing performance.
In one embodiment, the maleimide derivative is N-hydroxyethylmaleimide and/or N, N '- (4, 4' -methylenediphenyl) bismaleimide.
When the self-repairing polyurethane obtained by Diels-Alder reaction of N-hydroxyethyl maleimide and/or N, N '- (4, 4' -methylene diphenyl) bismaleimide and a furan ring grafted on the polyurethane is used for preparing the lithium ion battery, the obtained battery has more excellent ionic conductivity, cycle number and self-repairing performance.
In one embodiment, the inorganic nano-additive is graphene oxide and the other polymer is PVDF-HFP.
The graphene oxide and PVDF-HFP are grafted on the self-repairing polyurethane, and when the graphene oxide and PVDF-HFP are used for preparing the lithium ion battery, the obtained battery has more excellent ion conductivity, cycle times and self-repairing performance.
In one embodiment, the mass fraction of inorganic nano-additive is 0% to 10%, with typical but non-limiting mass fractions of inorganic nano-additive being 0%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, or 10%.
In one embodiment, the inorganic nano-additive is present in an amount of 0.5% to 5% by weight.
By reasonably adjusting and optimizing the mass fraction of the inorganic nano additive, when the obtained self-repairing polyurethane is used for preparing the lithium ion battery, the obtained battery has good ionic conductivity, cycle times and self-repairing performance.
In one embodiment, the inorganic nano-additive is present in an amount of 0.8% to 1.5% by weight.
By reasonably adjusting and optimizing the mass fraction of the inorganic nano additive, when the obtained self-repairing polyurethane is used for preparing the lithium ion battery, the obtained battery has more excellent ionic conductivity, cycle times and self-repairing performance.
In one embodiment, the self-repairing polyurethane has a mass fraction of 30% to 60%, preferably 40% to 50%; a typical but non-limiting mass fraction of the self-healing polyurethane is 30%, 32%, 34%, 36%, 38%, 40%, 42%, 44%, 46%, 48%, 50%, 52%, 54%, 56%, 58%, or 60%.
In one embodiment, the mass fraction of the other polymer is from 30% to 60%, preferably from 40% to 50%; typical but non-limiting mass fractions of other polymers are 30%, 32%, 34%, 36%, 38%, 40%, 42%, 44%, 46%, 48%, 50%, 52%, 54%, 56%, 58% or 60%.
According to a second aspect of the present invention, there is provided a method for preparing the self-repairing polymer electrolyte matrix, comprising the steps of:
grafting the inorganic nano additive and other polymers on the self-repairing polyurethane to obtain the self-repairing polymer electrolyte matrix.
The self-repairing polymer electrolyte matrix can be prepared by grafting the inorganic nano additive and other polymers on the self-repairing polyurethane. The preparation method is simple.
In one embodiment, a method of making a self-healing polymer electrolyte matrix includes the steps of:
(a) dissolving an inorganic nano additive in an organic solvent, then adding diisocyanate, and reacting to obtain a modified inorganic nano additive;
(b) adding a dihydroxy compound into the solution obtained in the step (a), and reacting to obtain polyurethane grafted with an inorganic nano additive;
(c) adding a furan derivative to step (b) to graft the furan derivative onto the polyurethane obtained in step (b);
(d) adding a maleimide derivative into the step (c) to enable the maleimide derivative and a furan derivative to generate Diels-Alder reaction, so as to obtain self-repairing polyurethane with dynamic covalent bonds;
(e) and (d) dissolving other polymers in an organic solvent, adding the solution in the step (d) to graft the other polymers on the self-repairing polyurethane obtained in the step (d), coating the self-repairing polyurethane on the surface of the substrate, and removing the solvent to obtain the self-repairing polymer electrolyte matrix.
In one embodiment, in step (a), the organic solvent comprises an amide-based organic solvent, preferably N, N-dimethylformamide; the diisocyanate includes at least one of 4,4 '-methylenebis (phenyl isocyanate), tolylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and lysine diisocyanate, and preferably 4, 4' -methylenebis (phenyl isocyanate); the reaction temperature is 75-95 ℃, the reaction time is 2-4h, and the reaction gas atmosphere is nitrogen; the feeding ratio of the inorganic nano additive, the organic solvent and the diisocyanate is 0-22: 40-60: 6-10mg/mL/mmol, preferably 20: 50: 8 mg/mL/mmol.
In step (b), the dihydroxy compound comprises a polyether polyol, preferably polytetrahydrofuran diol, more preferably polytetrahydrofuran diol having a number average molecular weight of 1500-2500; the reaction temperature is 75-95 ℃, the reaction time is 2-4h, and the reaction gas atmosphere is nitrogen; the molar ratio of the dihydroxy compound to the diisocyanate is 1: 1.8-2.5, preferably 1: 2.
in the step (c), the grafting temperature is 75-95 ℃, the grafting time is 2-4h, and the atmosphere of grafting gas is nitrogen; the molar ratio of furan derivative to diisocyanate is 6-6.5: 8, preferably 6.25: 8.
in the step (d), the reaction temperature is 75-95 ℃, the reaction time is 12-38h, and the reaction gas atmosphere is nitrogen; the molar ratio of the maleimide derivative to the furan derivative is 4-4.5: 6-6.5, preferably 4.2: 6.25.
in the step (e), the organic solvent comprises an amide organic solvent, preferably N, N-dimethylformamide, the grafting temperature is 60-100 ℃, and the grafting time is 1-12 h; the weight ratio of other polymers to the self-repairing polyurethane is 30-60: 30-60, preferably 40-50: 40-50.
According to a third aspect of the invention, a self-repairing polymer electrolyte is provided, which comprises the self-repairing polymer electrolyte matrix or the self-repairing polymer electrolyte matrix obtained by the preparation method, electrolyte salt and a solvent.
The self-repairing polymer electrolyte containing the self-repairing polymer electrolyte matrix has high working voltage, excellent electrochemical performance and good self-repairing performance, and the self-repairing polymer electrolyte is applied to the battery, so that the finally obtained battery has good flexibility, self-repairing performance and higher energy density, the safety and reliability of the flexible lithium ion battery are improved, the stability of energy storage and release under extreme environments is better, and the self-repairing polymer electrolyte has wide application prospect in the field of wearable electronic equipment.
The kind of the electrolyte salt is not particularly limited, and a lithium salt that is conventionally used in lithium ion batteries in the art may be used. For example, lithium hexafluorophosphate, lithium perchlorate, lithium tetrafluoroborate, lithium acetate, lithium salicylate, lithium acetoacetate, lithium carbonate, lithium trifluoromethanesulfonate, lithium dodecylsulfate, lithium citrate, lithium bis (trimethylsilyl) amide, lithium hexafluoroarsenate or lithium trifluoromethanesulfonylimide may be mentioned.
The kind of the solvent is not particularly limited, and an organic solvent or an ionic liquid that is conventionally used in lithium ion batteries in the art may be used. For example, the organic solvent may be an ester solvent, sulfone solvent, amide solvent, ether solvent or nitrile solvent; the ester solvent can be propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, butylene carbonate, dipropyl carbonate, methyl propyl carbonate, dibutyl carbonate, methyl butyl carbonate, methyl isopropyl carbonate, methyl ester, methyl formate, methyl acetate, fluoroethylene carbonate, methyl propionate, ethyl acetate, gamma-butyrolactone, ethylene sulfite, propylene sulfite, dimethyl sulfite or diethyl sulfite, and can be selected from propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate or ethyl methyl carbonate; the sulfone solvent may be dimethyl sulfone; the amide solvent can be N, N-dimethylacetamide; the ether solvent can be tetrahydrofuran, 2-methyltetrahydrofuran, 1, 3-dioxolane, 4-methyl-1, 3-dioxolane, dimethoxymethane, 1, 2-dimethoxyethane, 1, 2-dimethoxypropane, triethylene glycol dimethyl ether, dimethyl ether or crown ether; the ionic liquid may be 1-ethyl-3-methylimidazole-tetrafluoroborate, 1-ethyl-3-methylimidazole-hexafluorophosphate, 1-ethyl-3-methylimidazole-bistrifluoromethylsulfonyl imide salt, 1-propyl-3-methylimidazole-tetrafluoroborate, 1-propyl-3-methylimidazole-hexafluorophosphate, 1-propyl-3-methylimidazole-bistrifluoromethylsulfonyl imide salt, 1-butyl-1-methylimidazole-hexafluorophosphate, 1-butyl-1-methylimidazole-tetrafluoroborate, 1-butyl-1-methylimidazole-bistrifluoromethylsulfonyl imide salt, N-butyl-N-methylpyrrolidine-bistrifluoromethylsulfonyl imide salt, N-butyl-3-methylimidazole-tetrafluoroborate, 1-butyl-1-methylpyrrolidine-bistrifluoromethylsulfonyl imide salt, N-methyl-N-propylpyrrolidine-bistrifluoromethylsulfonyl imide salt, N-methyl, propylpiperidine-bistrifluoromethylsulfonyl imide salt or N-methyl, butylpiperidine-bistrifluoromethylsulfonyl imide salt. The concentration of the electrolyte salt in the electrolyte is 0.1-10 mol/L.
In one embodiment, the electrolyte salt is lithium hexafluorophosphate.
The self-repairing polymer electrolyte obtained by taking lithium hexafluorophosphate as electrolyte salt enables the finally obtained battery to have good ionic conductivity, cycle times and self-repairing performance.
In one embodiment, the concentration of the electrolyte salt in the electrolyte is 1 mol/L.
By reasonably adjusting and optimizing the addition of the electrolyte salt, the finally obtained battery has good ionic conductivity, cycle frequency and self-repairing performance.
According to a fourth aspect of the present invention, there is provided a method for preparing the self-repairing polymer electrolyte, comprising the steps of:
and immersing the self-repairing polymer electrolyte matrix in a solvent containing electrolyte salt, and adsorbing until the self-repairing polymer electrolyte matrix is saturated to obtain the self-repairing polymer electrolyte.
And immersing the self-repairing polymer electrolyte matrix in a solvent containing electrolyte salt, swelling and activating, adsorbing until the matrix is saturated, and wiping off redundant solvent to obtain the self-repairing polymer electrolyte. The preparation method is simple.
According to a fifth aspect of the present invention, there is provided a lithium ion battery comprising the self-healing polymer electrolyte described above, a positive electrode, and a negative electrode.
The lithium ion battery contains the repairing polymer electrolyte, has good flexibility and self-repairing performance and higher energy density, improves the safety and reliability of the flexible lithium ion battery, ensures that the stability of energy storage and release under extreme environments is better, and has wide application prospect in the field of wearable electronic equipment.
The kind of the active material of the positive electrode is not particularly limited, and active materials that are conventionally used in the art for positive electrodes of lithium ion batteries may be used. For example, lithium iron phosphate, lithium cobaltate, lithium manganate, lithium vanadium phosphate, lithium nickel cobalt manganate, or lithium nickel cobalt aluminate may be mentioned.
The kind of the active material of the negative electrode is not particularly limited, and an active material that is conventionally used for a negative electrode of a lithium ion battery in the art may be used. For example, it may be a metallic lithium sheet, graphite, mesocarbon fiber, mesocarbon microbeads, soft carbon, hard carbon, or silicon carbon composite.
The structural shape of the lithium ion battery is not limited, and the lithium ion battery can be a button cell battery, a columnar battery or a soft package battery.
According to a sixth aspect of the present invention, there is provided use of the above lithium ion battery in an electronic device, an electric tool, or an electric vehicle.
The lithium ion battery is applied to electronic equipment, electric tools or electric vehicles, can improve the safety and reliability of the electronic equipment, the electric tools or the electric vehicles,
in one embodiment, the application of the lithium ion battery in wearable electronic equipment is provided.
The lithium ion battery has high safety and reliability, so that the lithium ion battery has high stability of energy storage and release in extreme environments, and can be applied to wearable electronic equipment.
The technical solution of the present invention will be further described with reference to examples and comparative examples.
Example 1
1. Self-repairing polymer electrolyte matrix
A self-repairing polymer electrolyte matrix comprises graphene oxide (500 nm-2 μ M in size), self-repairing polyurethane and PVDF-HFP (Aldrich, M)w～455000,Mn110000); the graphene oxide and PVDF-HFP are grafted on the self-repairing polyurethane, and the self-repairing polyurethane is furan-maleimide structural self-repairing polyurethane.
2. Preparation of self-repairing polymer electrolyte matrix
The preparation method of the self-repairing polymer electrolyte matrix comprises the following steps:
(a) 20mg of graphene oxide was dissolved in 50mL of DMF (N, N-dimethylformamide), and 2.0g of 4, 4' -methylenebis (phenyl isocyanate) was added thereto at 80 ℃ under N2And carrying out protection reaction for 2h to obtain the modified inorganic nano additive.
(b) To the solution obtained in step (a), 8.0g of polytetrahydrofuran diol (PTMEG2000) was added and the mixture was dropped under N via a constant pressure dropping funnel2Adding the mixture into a reaction system drop by drop under protection, continuing to react for 2 hours at the temperature of 80 ℃, and obtaining the polyurethane grafted with the inorganic nano additive after reaction.
(c) 0.8g of 2, 5-furandimethanol was added to step (b) in N2And (b) protecting and continuing the reaction at 80 ℃ for 2 hours to graft the 2, 5-furandimethanol on the polyurethane obtained in the step (b).
(d) Adding 1.5g of N, N '- (4, 4' -methylenediphenyl) Bismaleimide (BMI) in the step (c), so that the BMI and the furan ring on the polyurethane obtained in the step (c) react in a Diels-Alder manner, and reacting in N2And (3) continuously reacting for 24 hours at the temperature of 80 ℃ under protection to obtain the self-repairing polyurethane with the dynamic covalent bond.
(e) And (3) dissolving 2g of PVDF-HFP in 20mL of DMF, stirring for 3h at the temperature of 80 ℃ to completely dissolve the PVDF-HFP in the DMF, then adding the solution in the step (d), stirring for 2h at the temperature of 80 ℃ to graft the PVDF-HFP on the self-repairing polyurethane obtained in the step (d), coating the obtained solution on a glass plate, putting the glass plate into an oven, heating for 24h at the temperature of 80 ℃ in vacuum, and removing the solvent to obtain the self-repairing polymer electrolyte matrix.
3. Self-repairing polymer electrolyte
A self-repairing polymer electrolyte comprises a self-repairing polymer electrolyte matrix, electrolyte salt and a solvent.
Preparation of self-repairing polymer electrolyte: immersing a self-healing polymer electrolyte matrix in a solution containing 1M lithium hexafluorophosphate (LiPF)6) The mixed solution is swelled and activated, adsorbed to saturation, and wiped to dry redundant solvent, so as to obtain the self-repairing polymer electrolyte.
Wherein the mixed solution is composed of EC, EMC and DMC in a volume ratio of EC to EMC to DMC of 1:1:1, and the solution containing electrolyte salt is marked as 1M LiPF6-EC:EMC:DMC(1:1:1)。
Examples 2 to 5
Examples 2 to 5 differ from example 1 only in the kind of furan derivative, and are specifically shown in table 1.
TABLE 1 Furan derivative species
Examples Class of furan derivatives
1 2, 5-Furan dimethanol
2 Furfuryl alcohol
3 Furfuryl amine
4 1, 6-hexamethylene-bis (2-furylmethyl carbamate)
5 Trifuryl diols
Examples 6 to 9
Examples 6 to 9 differ from example 1 only in the kind of maleimide derivative, as shown in Table 2.
TABLE 2 Maleimide derivative species
Examples Species of maleimide derivative
1 N, N '- (4, 4' -methylenediphenyl) bismaleimide
6 N-hydroxyethyl maleimide
7 M-600-Maleamide
8 D-400-Maleamide
9 T-403-Maleamide
Examples 10 to 12
Examples 10 to 12 differ from example 3 only in the kind of other polymers, as shown in Table 3.
TABLE 3 classes of other polymers
Figure BDA0001906659990000201
Figure BDA0001906659990000211
Examples 13 to 16
Examples 13-16 differ from example 1 only in the type of inorganic nano-additive, as shown in Table 4.
TABLE 4 kinds of inorganic Nanoadditives
Examples Kinds of inorganic Nanoindditives
1 Graphene oxide
13 Carbon nanotube
14 Nano Al2O3
15 Nano SiO2
16 Nano TiO 22
Examples 17 to 19
Examples 17-19 differed from example 1 only in the amount of inorganic nano-additive, as shown in Table 5.
TABLE 5 amount of inorganic nano-additives
Examples Mass fraction of inorganic nano material additive
1 1％
17 0％
18 5％
19 10％
Examples 20 to 24
Examples 20 to 24 differ from example 1 only in the solvent of the electrolyte salt or the concentration of the electrolyte salt, as shown in table 6.
TABLE 6 solvents and concentrations of electrolyte salts
Examples Solvent and concentration of electrolyte salt
1 1M LiPF6-EC:EMC:DMC(1:1:1)
20 1M LiPF6-EC:DEC(1:1)
21 1M LiPF6-EC:EMC:(1:1)
22 1M LiPF6-EC:DMC:(1:1)
23 1M LiPF6-EC:EMC:DEC(1:1:1)
24 1.5M LiPF6-EC:EMC:DMC(1:1:1)
Comparative example 1
1. Polymer electrolyte matrix
A polymer electrolyte matrix comprises graphene oxide (500 nm-2 μ M in size), polyurethane and PVDF-HFP (Aldrich, M)w～455000,Mn110000); graphene oxide and PVDF-HFP were grafted on the polyurethane.
2. Preparation of polymer electrolyte matrix
The preparation method of the polymer electrolyte matrix comprises the following steps:
(a) 20mg of graphene oxide was dissolved in 50mL of DMF (N, N-dimethylformamide), and 2.0g of 4, 4' -methylenebis (phenyl isocyanate) was added thereto at 80 ℃ under N2And carrying out protection reaction for 2h to obtain the modified inorganic nano additive.
(b) To the solution obtained in step (a), 8.0g of polytetrahydrofuran diol (PTMEG2000) was added and the mixture was dropped under N via a constant pressure dropping funnel2Adding the mixture into a reaction system drop by drop under protection, continuing to react for 2 hours at the temperature of 80 ℃, and obtaining the polyurethane grafted with the inorganic nano additive after reaction.
(c) Dissolving 2g of PVDF-HFP in 20mL of DMF, stirring at 80 ℃ for 3h to completely dissolve PVDF-HFP in DMF, adding the solution obtained in the step (b), stirring at 80 ℃ for 2h to graft PVDF-HFP on the polyurethane obtained in the step (b), coating the obtained solution on a glass plate, putting the glass plate into an oven, heating at 80 ℃ under vacuum for 24h, and removing the solvent to obtain the polymer electrolyte matrix.
3. Polymer electrolyte
A polymer electrolyte includes a polymer electrolyte matrix, an electrolyte salt, and a solvent.
Preparation of polymer electrolyte: immersing the polymer electrolyte matrix in a solution containing 1M lithium hexafluorophosphate (LiPF)6) The mixed solution is swelled and activated, adsorbed to saturation, and wiped to dry the redundant solvent, so as to obtain the polymer electrolyte.
Wherein the mixed solution is composed of EC, EMC and DMC in a volume ratio of EC to EMC to DMC of 1:1:1, and the solution containing electrolyte salt is marked as 1M LiPF6-EC:EMC:DMC(1:1:1)。
Test example 1
1. The self-repairing polymer electrolytes prepared in examples 1 to 24 and the polymer electrolyte prepared in comparative example 1 were subjected to a room temperature conductivity test, which was carried out by the following methods: and assembling the button cell, testing the electrochemical impedance of the polymer electrolyte membrane, and calculating the conductivity according to a calculation formula rho ═ RS/L. The test results are shown in table 7.
2. The self-repairing polymer electrolytes prepared in examples 1 to 24 and the polymer electrolyte prepared in comparative example 1 are subjected to a self-repairing performance test, and the test method comprises the following steps: after the polymer electrolyte is cut into two parts, the polymer electrolyte is heated and repaired for 1h at the temperature of 60 ℃, the fracture part is repaired if completely healed, and the fracture part is not repaired if not completely healed. The test results are shown in table 7.
3. The lithium ion batteries in which the self-healing polymer electrolytes prepared in examples 1 to 24 and the polymer electrolyte prepared in comparative example 1 were assembled: and (3) sequentially assembling a lithium iron phosphate anode, a self-repairing polymer electrolyte and a graphite cathode into a sandwich structure, and sealing on a punching machine to prepare the button cell. After standing for 12h, the charge and discharge test is carried out under the conditions of multiplying power of 0.5C and voltage of 2.5-4V. The results of the number of cycles (capacity > 90%) obtained are shown in Table 7.
TABLE 7 Ionic conductivity, cycle number and self-healing Performance
Figure BDA0001906659990000241
Figure BDA0001906659990000251
The self-repairing polymer electrolyte obtained in example 1 has the conductivity as high as 2.8 multiplied by 10-3S/cm, and has higher room temperature conductivity. The material has good flexibility and good self-repairing performance, and when the polymer electrolyte is cut into two halves, the polymer electrolyte is heated and repaired for 1 hour at 60 ℃ and is brokenThe fissure is completely healed, and the mechanical property can reach more than 80 percent of the previous mechanical property. After 1500 cycles, the capacity retention of the battery of example 1 is greater than 90%, which indicates that the lithium ion battery based on the self-repairing polymer electrolyte has good electrochemical stability.
From examples 1 to 5, it is found that when the furan derivative is 2, 5-furandimethanol (example 1) or trifuryl diol (example 5), the obtained self-healing polymer electrolyte has more excellent ionic conductivity and self-healing performance, and the obtained battery has more excellent cycle number.
As can be seen from examples 1 and 6 to 9, when the maleimide derivative is N, N '- (4, 4' -methylenediphenyl) bismaleimide (example 1) or N-hydroxyethylmaleimide (example 6), the obtained self-healing polymer electrolyte has more excellent ionic conductivity and self-healing performance, and the obtained battery has more excellent cycle number.
According to the examples 1 and 10 to 12, when the other polymer is PVDF-HFP (example 1), the obtained self-repairing polymer electrolyte has more excellent ionic conductivity and self-repairing performance, and the obtained battery has more excellent cycle number.
As can be seen from examples 1 and 13 to 16, when the inorganic nano-additive is graphene oxide (example 1), the obtained self-repairing polymer electrolyte has more excellent ionic conductivity and self-repairing performance, and the obtained battery has more excellent cycle number.
It can be seen from examples 1 and 17 to 19 that the self-repairing polymer electrolyte obtained when the amount of the inorganic nano-additive is 1% to 5% is superior in performance, and when the amount of the inorganic nano-additive is less than 1% (example 1) is superior in ionic conductivity and self-repairing performance, and the battery obtained is superior in cycle number.
From examples 1 and 20 to 24, it is understood that the electrolyte salt solvent is EC: EMC: DMC (1:1:1) (example 1) or EC: EMC: DEC (1:1:1) (example 23), the performance is better, the electrolyte salt concentration is 1.5M (example 24), the self-repairing polymer electrolyte obtained in example 1 has more excellent ionic conductivity and self-repairing performance, and the obtained battery has more excellent cycle number.
According to example 1 and comparative example 1, the polyurethane of comparative example 1 does not contain furan-maleimide dynamic covalent bonds, the cycle number of the obtained battery is greatly reduced, example 1 can be cycled for 1500 times, while comparative example 1 only has 300 times, and the polymer electrolyte of comparative example 1 cannot be repaired after being fractured.
It should be understood that the contents not described in detail in the description of the above preparation method are common parameters that can be easily conceived by those skilled in the art, and thus the detailed description thereof may be omitted.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (7)

1. A self-healing polymer electrolyte matrix comprising an inorganic nano-additive, a self-healing polyurethane, and other polymers;
wherein the inorganic nano-additive and other polymers are grafted onto the self-healing polyurethane;
the self-repairing polyurethane is obtained through a Diels-Alder reaction;
the Diels-Alder reaction is a furan/maleimide Diels-Alder cycloaddition reaction;
grafting a furan derivative on polyurethane to obtain furan ring graft modified polyurethane, and then carrying out Diels-Alder reaction on the furan ring graft modified polyurethane and a maleimide derivative to obtain self-repairing polyurethane;
wherein the terminal groups of the polyurethane comprise isocyanate groups;
the furan derivative is 2, 5-furandimethanol;
the maleimide derivative is N-hydroxyethyl maleimide;
the inorganic nano additive is graphene oxide;
the other polymer is PVDF-HFP;
the mass fraction of the inorganic nano additive is 1 percent;
the mass fraction of the self-repairing polyurethane is 30-60%;
the mass fraction of the other polymer is 30-60%.
2. The method of making a self-healing polymer electrolyte matrix of claim 1, comprising the steps of:
grafting inorganic nano additive and other polymers on self-repairing polyurethane to obtain a self-repairing polymer electrolyte matrix;
the preparation method of the self-repairing polymer electrolyte matrix comprises the following steps:
(a) dispersing the inorganic nano additive into an organic solvent, then adding diisocyanate, and reacting to obtain a modified inorganic nano additive;
(b) adding a dihydroxy compound into the solution obtained in the step (a), and reacting to obtain polyurethane grafted with an inorganic nano additive;
(c) adding a furan derivative to step (b) to graft the furan derivative onto the polyurethane obtained in step (b);
(d) adding a maleimide derivative into the step (c) to enable the maleimide derivative and a furan derivative to generate Diels-Alder reaction, so as to obtain self-repairing polyurethane with dynamic covalent bonds;
(e) dissolving other polymers in an organic solvent, adding the solution obtained in the step (d) to graft the other polymers on the self-repairing polyurethane obtained in the step (d), coating the self-repairing polyurethane on the surface of the substrate, and removing the solvent to obtain a self-repairing polymer electrolyte matrix;
in the step (a), the organic solvent comprises an amide organic solvent;
and/or, in step (a), the diisocyanate comprises at least one of 4, 4' -methylenebis (phenyl isocyanate), toluene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and lysine diisocyanate;
and/or in the step (a), the reaction temperature is 75-95 ℃, the reaction time is 2-4h, and the reaction gas atmosphere is nitrogen;
and/or, in step (b), the dihydroxy compound comprises a polyether polyol;
and/or in the step (b), the reaction temperature is 75-95 ℃, the reaction time is 2-4h, and the reaction gas atmosphere is nitrogen;
and/or, in step (b), the molar ratio of the dihydroxy compound to the diisocyanate is 1: 1.8-2.5;
and/or in the step (c), the grafting temperature is 75-95 ℃, the grafting time is 2-4h, and the grafting gas atmosphere is nitrogen;
and/or, in step (c), the molar ratio of furan derivative to diisocyanate is 6-6.5: 8;
and/or in the step (d), the reaction temperature is 75-95 ℃, the reaction time is 12-38h, and the gas atmosphere of the reaction is nitrogen;
and/or, in step (d), the molar ratio of maleimide derivative to furan derivative is 4-4.5: 6-6.5;
and/or, in step (e), the organic solvent comprises an amide organic solvent;
and/or, in the step (e), the grafting temperature is 60-100 ℃, and the grafting time is 1-12 h;
and/or, in the step (e), the weight ratio of the other polymer to the self-repairing polyurethane is 30-60: 30-60.
3. A self-repairing polymer electrolyte is characterized by comprising the self-repairing polymer electrolyte matrix of claim 1 or the self-repairing polymer electrolyte matrix prepared by the preparation method of claim 2, an electrolyte salt and a solvent.
4. The self-healing polymer electrolyte of claim 3, wherein the electrolyte salt includes a lithium salt that is at least one of lithium hexafluorophosphate, lithium perchlorate, lithium tetrafluoroborate, lithium acetate, lithium salicylate, lithium acetoacetate, lithium carbonate, lithium trifluoromethanesulfonate, lithium dodecylsulfate, lithium citrate, lithium bis (trimethylsilyl) amide, lithium hexafluoroarsenate, and lithium trifluoromethanesulfonylimide;
the solvent comprises an organic solvent or an ionic liquid;
the organic solvent comprises at least one of an ester solvent, a sulfone solvent, an amide solvent, an ether solvent and a nitrile solvent;
the ester solvent comprises at least one of propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, butylene carbonate, dipropyl carbonate, methyl propyl carbonate, dibutyl carbonate, methyl butyl carbonate, methyl isopropyl carbonate, methyl ester, methyl formate, methyl acetate, fluoroethylene carbonate, methyl propionate, ethyl acetate, gamma-butyrolactone, ethylene sulfite, propylene sulfite, dimethyl sulfite and diethyl sulfite;
the sulfone solvent comprises dimethyl sulfone;
the amide solvent comprises N, N-dimethylacetamide;
the ether solvent comprises at least one of tetrahydrofuran, 2-methyltetrahydrofuran, 1, 3-dioxolane, 4-methyl-1, 3-dioxolane, dimethoxymethane, 1, 2-dimethoxyethane, 1, 2-dimethoxypropane, triethylene glycol dimethyl ether, dimethyl ether and crown ether;
the ionic liquid comprises 1-ethyl-3-methylimidazole-tetrafluoroborate, 1-ethyl-3-methylimidazole-hexafluorophosphate, 1-ethyl-3-methylimidazole-bistrifluoromethylsulfonyl imide salt, 1-propyl-3-methylimidazole-tetrafluoroborate, 1-propyl-3-methylimidazole-hexafluorophosphate, 1-propyl-3-methylimidazole-bistrifluoromethylsulfonyl imide salt, 1-butyl-1-methylimidazole-hexafluorophosphate, 1-butyl-1-methylimidazole-tetrafluoroborate, 1-butyl-1-methylimidazole-bistrifluoromethylsulfonyl imide salt, a salt of a compound of formula (I), At least one of N-butyl-N-methylpyrrolidine-bistrifluoromethylsulfonyl imide salt, 1-butyl-1-methylpyrrolidine-bistrifluoromethylsulfonyl imide salt, N-methyl-N-propylpyrrolidine-bistrifluoromethylsulfonyl imide salt, N-methyl, propylpiperidine-bistrifluoromethylsulfonyl imide salt, and N-methyl, butylpiperidine-bistrifluoromethylsulfonyl imide salt;
the concentration of the electrolyte salt in the electrolyte is 0.1-10 mol/L.
5. The method for preparing the self-repairing polymer electrolyte of claim 3 or 4, which is characterized by comprising the following steps:
and immersing the self-repairing polymer electrolyte matrix in a solvent containing electrolyte salt, and adsorbing until the self-repairing polymer electrolyte matrix is saturated to obtain the self-repairing polymer electrolyte.
6. A lithium ion battery comprising the self-healing polymer electrolyte of claim 3 or 4, a positive electrode, and a negative electrode;
the active material of the positive electrode comprises at least one of lithium iron phosphate, lithium cobaltate, lithium manganate, lithium vanadium phosphate, lithium nickel cobalt manganate and lithium nickel cobalt aluminate;
the active material of the negative electrode comprises at least one of metallic lithium sheets, graphite, mesocarbon fibers, mesocarbon microbeads, soft carbon, hard carbon and silicon-carbon composite materials.
7. Use of the lithium ion battery of claim 6 in an electronic device, an electric tool, or an electric vehicle;
the electronic device is a wearable electronic device.
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